CN106987101A - Polymer blend and preparation method thereof - Google Patents
Polymer blend and preparation method thereof Download PDFInfo
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- CN106987101A CN106987101A CN201710193927.5A CN201710193927A CN106987101A CN 106987101 A CN106987101 A CN 106987101A CN 201710193927 A CN201710193927 A CN 201710193927A CN 106987101 A CN106987101 A CN 106987101A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The present invention relates to a kind of polymer blend and preparation method thereof.The polymer blend is prepared from the following materials：The cyclohexanedimethanoester ester of poly terephthalic acid 1,4 (PCT) resin, glass fibre, nucleator A, nucleator B, toughener, antioxidant, lubricant, additive.The number-average molecular weight of the cyclohexanedimethanoester ester of poly terephthalic acid 1,4 (PCT) resin is 25000~30000；The nucleator A is carboxylic acid sodium salt organic micromolecule nucleator, and molecular weight is 100~200g/mol；The nucleator B is ionomer salt nucleator.The polymer blend crystalline rate of the present invention is faster, so that the molding time of material shortens, time cost during finished product processing is saved, and while crystalline rate is largely improved, the combination properties such as the impact property, bending property, heat-resistant deforming temperature of material can be preferably improved again.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of polymer blend and preparation method thereof.
Background technology
Polyester is the polymer general name as obtained by polyalcohol and polyacid polycondensation, refers mainly to PET
(PET), poly terephthalic acid 1,4- fourths diester (PBT), poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT), poly- naphthalene two
Acid cyclohexyl alkane diformazan alcohol ester (PCN), PEN (PEN) and their copolyester.These polyester phases
To cheap, and because their aromatic substances content is higher, therefore with high glass-transition temperature (Tg), this is given by it
The formed article that is made good heat resistance, rigidity and toughness.But, because crystalline rate is slow, limit polyester use and
Promote, especially poly terephthalic acid 1,4-CHDM ester (PCT).
Poly terephthalic acid 1,4-CHDM ester (PCT) is new engineering resin, and it not only has water absorption rate
The advantage for the polyester material such as relatively low, good stability of the dimension, resistance to chemical reagents be excellent, but also penetrated with the good transparency and resistance to y
Linearly, its most prominent advantage is that heat resistance is substantially better than PBT, PET engineering plastics, is current heat resistance highest thermoplastic
Property polyester, heat resistance can be equal to PPS phases, while it also has the excellent crystallization rate and low pitting not available for PPS,
Price is also cheap compared with PPS, therefore, with certain Development volue.But, poly terephthalic acid Isosorbide-5-Nitrae-cyclohexane dicarboxylates
(PCT) crystal property is still undesirable, and its crystalline rate not only influences the cycle of its processing and forming, and it is anti-to directly affect it
The physical and mechanical properties such as tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance.
At present, some researchs, such as patent CN100577730C have been done in the improvement in the prior art to crystallizing polyester speed
A kind of method for improving poly terephthalic acid diol ester crystalline rate is disclosed, but this method is directed to the crystallization of PET resin
The raising of speed.It is by the isophthalic two containing alkali metal sulfonate substituent that patent CN101987911A, which is disclosed using strand,
Formic acid replaces the high molecular nucleating agent connected and composed with straight chain type both-end hydroxyl two kinds of construction units of alcohol, to improve poly- 2,6- naphthalenes two
The method of formic acid glycol ester crystalline rate.Patent CN103849125A improves poly- by adding inorganic nucleator, to a certain degree
The crystalline rate of ester composition.
The content of the invention
Based on this, have short molding cycle, crystallization degree height, mechanical performance high, resistance to it is an object of the invention to provide one kind
Hot high polymer blend, can be applied in high temperature resistant, the electric part of high optical reflectance, such as：Projector equipment or lamp
Reflection timbering material of tool etc..
To reach above-mentioned purpose, the present invention uses following scheme：
A kind of polymer blend, is prepared from by the raw material of following parts by weight：
The number-average molecular weight of the poly terephthalic acid 1,4 cyclohexane dimethanol ester resin is 25000~30000.
The nucleator A is carboxylic acid sodium salt organic micromolecule nucleator, and molecular weight is 100~200g/mol.
The nucleator B is ionomer salt nucleator.
In one of the embodiments, the polymer blend is prepared from by the raw material of following parts by weight：
In one of the embodiments, described toughener is EPDM copolymer rubber (EPDM), Butadiene/Styrene
Block copolymer (SBS), polyolefin thermoelastic (POE) or ethylene-vinyl acetate copolymer.
In one of the embodiments, the antioxidant includes Hinered phenols antioxidant and the phosphorous acid esters antioxygen
Agent.
In one of the embodiments, the Hinered phenols antioxidant is four (β-(3,5- di-tert-butyl-hydroxy phenyls)
Propionic acid) pentaerythritol ester and/or β-(4- hydroxy phenyl -3,5- di-t-butyls) positive octadecanol ester of propionic acid；The phosphite ester
Kind antioxidant is phosphorous acid three (2,4- di-tert-butyl-phenyls) ester.
In one of the embodiments, in parts by weight, the antioxidant includes 0.1~1 part of Hinered phenols antioxidant, with
And 0.1~1 part of phosphite ester kind antioxidant.
In one of the embodiments, the glass fibre is alkali-free glass fibre, and the alkali-free glass fibre is continuous fine
Dimension and/or chopped strand.
In one of the embodiments, the lubricant is pentaerythritol stearate.
In one of the embodiments, in parts by weight, the additive includes 1~30 part of Chinese white, and fluorescence
0.03~0.08 part of brightening agent.
In one of the embodiments, the Chinese white is Sb2O3、ZnO、TiO2、ZnS、BaSO4、CaCO3In one kind
Or it is several.
In one of the embodiments, described fluorescent whitening agent is double (5 methyl -2- benzoxazolyls) the hexichol second of 4,4-
Alkene.
The present invention also provides described polymer blend preparation method, comprises the following steps：
(1) poly terephthalic acid 1,4-CHDM ester (PCT) resin is placed in 100~120 DEG C, dries 4
After~12 hours, cooling；Poly terephthalic acid 1,4 cyclohexane dimethanol ester (PCT) resin and the toughener after cooling down
It is added in homogenizer and is pre-mixed；
(2) the nucleator A, nucleator B, antioxidant, lubricant and additive are added to another homogenizer
It is middle to be mixed, then obtained mixture is added in step (1) described homogenizer and mixed；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 260
~310 DEG C, two area's temperature：280~330 DEG C, three area's temperature are 280~330 DEG C, four area's temperature：280~330 DEG C, five area's temperature
For 280~330 DEG C, six area's temperature：280~330 DEG C, die head temperature：280~325 DEG C, driving screw rotating speed is：100~
450rpm。
In one of the embodiments, in the step (1), by the poly terephthalic acid 1,4-CHDM ester
(PCT) resin is placed in 110 DEG C, dries 4~6 hours；In the step (3), the technological parameter is：One area's temperature be 270~
300 DEG C, two area's temperature：290~325 DEG C, three area's temperature are 290~325 DEG C, four area's temperature：290~325 DEG C, five area's temperature are
290~325 DEG C, six area's temperature：290~325 DEG C, die head temperature：290~325 DEG C, driving screw rotating speed is：250~450rpm.
In one of the embodiments, the screw configuration of the parallel double-screw extruder is single thread；Spiro rod length L
It is 30~60 with the ratio between diameter D L/D；The screw rod is provided with more than one gear block area and more than one left-hand thread area.
In one of the embodiments, the ratio between described spiro rod length L and diameter D L/D are 40~55；The screw rod is provided with
2 gear block areas and 2 left-hand thread areas.
The principle and advantage of the present invention is as follows：
The nucleation of high polymer includes primary nucleation and secondary nucleation.Wherein primary nucleation be divided into again homogeneous nucleation and out-phase into
There are both mechanism of nucleation simultaneously in two kinds of core, general polymerization thing.By molecular melt segment, itself warm-up movement is produced homogeneous nucleation
The chain bundle or folded chain of ordered arrangement are as nucleus, and nucleus is continuously generated in whole process, therefore the nucleus developed into
It is not of uniform size, required temperature is generally than relatively low.Heterogeneous nucleation is impurity, artificially polymer crystals, the addition point come in addition
Centered on scattered small particles or chamber wall, adsorpting polymerization thing segment makees ordered arrangement and forms nucleus, and heterogeneous nucleation is by temperature shadow
Sound is smaller, can occur at a higher temperature.So to improve crystalline rate, it is necessary to increase its heterogeneous nucleation ability.
The present invention is by selecting rational ionomer and organic molecule nucleator, and content is used both interworking, is obtained
Obtained poly terephthalic acid 1,4-CHDM ester (PCT) resin material of more highly crystalline speed.So as to prepare shaping
The preferable engineering polyester plasticses of combination property such as the time is short, its good mechanical performance, heat resistance height.Wherein, organic molecule
The mechanism of nucleation of nucleator is mainly relevant with its chemical constitution, and PCT can occur chemical anti-when being extruded at high temperature with carboxylic acid sodium salt
Should, ion cluster can be formed between PCT-COONa materials, the PCT melts with ionic end groups by generating, and ion cluster will turn into nucleation
Agent serves nucleation, the regular arrangement rapid crystallization of strand in the melt.Ionomer is ionomer, is conventional one
High molecular nucleating agent is planted, refers to and a small amount of ionogen is carried on high polymer main chain, key component is by non-ionic skeleton
Chain and a small amount of component containing ion are constituted.Compared with organic molecule nucleator, ionomer nucleator is with ionic end groups
Macromolecular generation while, the also PCT-R flexible group of organic nucleating agent (R be) generations, because R strands are than PCT points
The flexible effect for more preferably serving accelerator again in system of subchain, its introducing promotes PCT molecular motion, reduces point
Subchain diffuses into the free energy of lattice.In both compounding uses, organic molecule nucleator plays main nucleation, and
Ionomer nucleator reduces the free energy help nucleus growth that strand diffuses into lattice by introducing flexible group, the two
Synergistic effect is reached, PCT crystalline rate is further improved.
Compared with prior art, the present invention has the advantages that：
1st, polymer blend crystalline rate of the invention faster, so that the molding time of material shortens, saves finished product
Time cost during processing, and largely improve crystalline rate while, can preferably improve again material impact property,
The combination properties such as bending property, heat-resistant deforming temperature.
2nd, above-mentioned polymer blend is prepared using the preparation method of the polymer blend of the present invention, its technique is simple, it is easy to
Control, not high to equipment requirement, used equipment is general polymer-processing equipment, invests not high, and due to preferable
Dispersiveness make it that material settling out performance is high.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of polymer blend described in one embodiment of the invention.
Embodiment
For the feature, technological means and the specific purposes reached, function of the present invention can be further appreciated that, this hair is parsed
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of polymer blend of the present invention is as follows：
Raw material used in the embodiment of the present invention is as follows, and preparation technology flow chart is see Fig. 1：
Poly terephthalic acid 1,4-CHDM ester (PCT) resin, number-average molecular weight is about 28000, selected from the U.S.
Yisiman Chemical Company；
Nucleator A, is carboxylic acid sodium salt, and molecular weight is 100~200g/mol, is a kind of organic molecule nucleator, choosing
From Chinese medicines group Solution on Chemical Reagents in Shanghai Co., Ltd；
Nucleator B, is ionomer8920, it is a kind of sodium-ion type thermoplasticity ionomer, selected from the U.S.
E.I.Du Pont Company；
Glass fibre, diameter is at 12~23 μm, including continuous fiber and chopped strand, public selected from U.S.'s OWENS CORNING
Department；
Chinese white, average grain diameter is in 0.2~0.3um, and D50 is less than 0.25um, selected from du pont company；
Toughener, Butadiene/Styrene block copolymer (SBS), styrene proportion is 30~50%, selected from yueyang, hunan
Petrochemical industry；
Four (β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters (antioxidant 1010), are used as main antioxygen
Agent, selected from Ciba of Switzerland；
Phosphorous acid three (2,4- di-tert-butyl-phenyl) ester (irgasfos 168), as auxiliary antioxidant, selected from Switzerland's vapour Bagong
Department；
Pentaerythritol stearate (lubricant), selected from U.S.'s Clariant Corporation；
4,4- double (5 methyl -2- benzoxazolyls) talan (fluorescent whitening agent), selected from U.S.'s Clariant Corporation.
Embodiment 1：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Embodiment 2：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, lubricant
And fluorescent whitening agent is added in another homogenizer and mixed, and obtained mixture then is added into step (1)
Described in mixed in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 295
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：315 DEG C, five area's temperature are 315 DEG C, six area's temperature：315
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 55,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Embodiment 3：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by the PCT resins and toughness reinforcing after cooling
Agent is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Embodiment 4：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 295
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：315 DEG C, five area's temperature are 315 DEG C, six area's temperature：315
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：400rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Embodiment 5：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Comparative example 1：
A kind of polymer blend of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Comparative example 2：
A kind of polymer blend of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Comparative example 3：
A kind of polymer blend of this comparative example, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is double thread, and the ratio between spiro rod length L and diameter D L/D are 45,
The screw rod is provided with 1 gear block area, no left-hand thread area.
Comparative example 4：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 310 DEG C, four area's temperature：310 DEG C, five area's temperature are 310 DEG C, six area's temperature：310
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 50,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
Comparative example 5：
A kind of polymer blend of the present embodiment, is prepared from by the following raw material：
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
(1) the PCT resins are placed in 110 DEG C, after drying 6 hours, cooling, by PCT resins after cooling and described
Toughener is added in homogenizer and is pre-mixed；
(2) by the Chinese white, nucleator A, nucleator B, Hinered phenols antioxidant, phosphite ester kind antioxidant, profit
Lubrication prescription and fluorescent whitening agent are added in another homogenizer and mixed, and obtained mixture then is added into step
(1) mixed described in homogenizer；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and by the glass fibre from institute
The lateral feeding for stating parallel double-screw extruder adds progress melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 300
DEG C, two area's temperature：310 DEG C, three area's temperature are 315 DEG C, four area's temperature：315 DEG C, five area's temperature are 315 DEG C, six area's temperature：315
DEG C, die head temperature：310 DEG C, driving screw rotating speed is：350rpm.
The screw configuration of the parallel double-screw extruder is single thread, and the ratio between spiro rod length L and diameter D L/D are 55,
The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
It is below comparative example and embodiment list：
The comparative example of table 1 constitutes parts by weight list with embodiment raw material
Above-mentioned comparative example and the made sample of embodiment are subjected to following performance test：
Tensile property：By ASTM D-638 standard testings, rate of extension 50mm/min；
Notched impact properties：By ASTM D-256 standard testings, batten is band breach；
HDT：By ASTM D648 (1.82MPa) standard testing, thickness of test piece 6.0mm；
Degree of supercooling (Δ T)：Tested, tested according to GB/T 19466-2004 standards using DSC.Degree of supercooling (Δ T) is
Melting temperature (Tm) and thermal crystalline peak temperature (Tp) difference, its implication be degree of supercooling it is smaller, the crystalline rate of its polymer is got over
It hurry up.
The comparative example of table 2 and embodiment performance list
As shown in Table 1, comparative example 1 is the polymer blend of non-Added Nucleating Agents；Comparative example 4 is addition organic molecule nucleation
The polymer blend of agent.By contrast as can be seen that adding the degree of supercooling of the polymer blend of organic molecule nucleator has bright
It is aobvious to reduce, show that its crystalline rate is improved, its tensile strength, notch impact strength and HDT are better than non-Added Nucleating Agents
Polymer blend, because the raising of crystalline rate brings crystallinity also accordingly to improve, so as to bring above mechanics and heat-resisting
Performance improvement.Comparative example 5 is the polymer blend for adding ionomer sodium salt.Gathered by contrast as can be seen that adding ion
The degree of supercooling of the polymer blend of compound sodium salt is obviously reduced, and shows that its crystalline rate is improved, its tensile strength, breach
Impact strength and HDT are better than the polymer blend of non-Added Nucleating Agents, show that the ionomer sodium salt also contributes to raising group
The crystalline rate of compound.
Comparative example 2 is the polymer blend for not adding toughener；Embodiment 3 is the polymer blend for adding toughener, the two
Remaining recipe ingredient is identical and all uses interworking nucleator.By contrast as can be seen that adding the polymer blend of toughener
Quite, the addition of toughener is favorably improved its toughness to notch impact strength bigger, remaining performance, and the nucleator is to remaining
Performance slightly has influence but little.
Comparative example 3 is that screw configuration is double thread, and the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is provided with 1
Gear block area, the polymer blend that the double screw extruder in no left-hand thread area is prepared；Embodiment 3 is that screw configuration is single line
Screw thread, the ratio between spiro rod length L and diameter D L/D is 50, and twin-screw of the screw rod provided with 2 gear block areas and 2 left-hand thread areas is squeezed
Go out the polycarbonate compositions that machine is prepared.Both formulas are consistent.By contrast as can be seen that using the screw rod of the present invention
Single thread is shaped as, the ratio between spiro rod length L and diameter D L/D are 50, and screw rod is provided with 2 gear block areas and 2 left-hand thread areas
When, the degree of supercooling of polymer blend is lower, and tensile strength, notch impact strength and HDT are higher, and the screw combinations are more suitable for this
The processing of composition.
Comparative example 1-5 and comparative example 4-5, has found to add the nucleator (embodiment 1-5) of interworking than certain is used alone
Kind nucleator is better, and degree of supercooling is lower than comparative example 4-5, shows that crystalline rate is further carried after its interworking
It is high.
Comparative example 1-5, the degree of supercooling of embodiment 3 is minimum, and the performance such as tensile strength, notch impact strength and HDT is more
Good, the combination property of embodiment 3 is optimal；It is indicated above adding the nucleator ratio organic molecule of interworking：Ionomer sodium
Salt is about 0.5:The highly crystalline speed polymer blend of optimal synthesis performance can be obtained when 0.5.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of polymer blend, it is characterised in that be prepared from by the raw material of following parts by weight：
The number-average molecular weight of the poly terephthalic acid 1,4 cyclohexane dimethanol ester resin is 25000~30000；
The nucleator A is carboxylic acid sodium salt organic micromolecule nucleator, and molecular weight is 100~200g/mol；
The nucleator B is ionomer salt nucleator.
2. polymer blend according to claim 1, it is characterised in that be prepared from by the raw material of following parts by weight：
3. polymer blend according to claim 1, it is characterised in that described toughener is EPDM copolymerization rubber
Glue, Butadiene/Styrene block copolymer, polyolefin thermoelastic or ethylene-vinyl acetate copolymer.
4. polymer blend according to claim 1, it is characterised in that the antioxidant include Hinered phenols antioxidant and
The phosphite ester kind antioxidant.
5. polymer blend according to claim 4, it is characterised in that the Hinered phenols antioxidant is four (β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or β-(4- hydroxy phenyl -3,5- di-t-butyls) propionic acid positive 18
Carbon alcohol ester；The phosphite ester kind antioxidant is phosphorous acid three (2,4- di-tert-butyl-phenyls) ester.
6. polymer blend according to claim 1, it is characterised in that the glass fibre is alkali-free glass fibre, should
Alkali-free glass fibre is continuous fiber and/or chopped strand.
7. the polymer blend preparation method described in claim any one of 1-6, and be characterised by, comprise the following steps：
(1) the poly terephthalic acid 1,4-CHDM ester resin is placed in 100~120 DEG C, dried 4~12 hours
Afterwards, cool down, the poly terephthalic acid 1,4-CHDM ester resin and the toughener after cooling are added at a high speed
It is pre-mixed in mixer；
(2) the nucleator A, nucleator B, antioxidant, lubricant and additive are added in another homogenizer
Obtained mixture, is then added in step (1) described homogenizer and is mixed by row mixing；
(3) mixture for mixing step (2) is placed in parallel double-screw extruder, and the glass fibre is put down from described
The lateral feeding of row double screw extruder, which is added, carries out melting extrusion, and granulation, technological parameter is as follows：One area's temperature is 260~310
DEG C, two area's temperature：280~330 DEG C, three area's temperature are 280~330 DEG C, four area's temperature：280~330 DEG C, five area's temperature are 280
~330 DEG C, six area's temperature：280~330 DEG C, die head temperature：280~325 DEG C, driving screw rotating speed is：100~450rpm.
8. polymer blend preparation method according to claim 7, it is characterised in that in the step (1), will be described poly-
Terephthalic acid (TPA) 1,4-CHDM ester resin is placed in 110 DEG C, dries 4~6 hours；In the step (3), the technique
Parameter is：One area's temperature is 270~300 DEG C, two area's temperature：290~325 DEG C, three area's temperature are 290~325 DEG C, four area's temperature
Degree：290~325 DEG C, five area's temperature are 290~325 DEG C, six area's temperature：290~325 DEG C, die head temperature：It is 290~325 DEG C, main
Screw speed is：250~450rpm.
9. the polymer blend preparation method according to claim 7 or 8, it is characterised in that the parallel double-screw extrusion
The screw configuration of machine is single thread；The ratio between spiro rod length L and diameter D L/D are 30~60；The screw rod is provided with more than one
Gear block area and more than one left-hand thread area.
10. polymer blend preparation method according to claim 9, it is characterised in that the spiro rod length L and diameter D
The ratio between L/D be 40~55；The screw rod is provided with 2 gear block areas and 2 left-hand thread areas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875936A (en) * | 2020-06-19 | 2020-11-03 | 金发科技股份有限公司 | Polyester resin composition, molded product prepared from same and application of molded product |
| CN114940813A (en) * | 2022-06-30 | 2022-08-26 | 广东中塑新材料有限公司 | PBT-based luminescent composite material and preparation method thereof |
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| CN101787184A (en) * | 2009-12-30 | 2010-07-28 | 中国石油化工股份有限公司 | Quickly crystallized polyester engineering plastic and preparation method thereof |
| CN102040811A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polycaprolactam (PCT) engineering plastics and preparation method thereof |
| CN103589121A (en) * | 2012-08-14 | 2014-02-19 | 苏州汉扬精密电子有限公司 | Glass fiber reinforced PCT resin and preparation method thereof |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787184A (en) * | 2009-12-30 | 2010-07-28 | 中国石油化工股份有限公司 | Quickly crystallized polyester engineering plastic and preparation method thereof |
| CN102040811A (en) * | 2010-12-29 | 2011-05-04 | 深圳市科聚新材料有限公司 | Polycaprolactam (PCT) engineering plastics and preparation method thereof |
| CN103589121A (en) * | 2012-08-14 | 2014-02-19 | 苏州汉扬精密电子有限公司 | Glass fiber reinforced PCT resin and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875936A (en) * | 2020-06-19 | 2020-11-03 | 金发科技股份有限公司 | Polyester resin composition, molded product prepared from same and application of molded product |
| CN114940813A (en) * | 2022-06-30 | 2022-08-26 | 广东中塑新材料有限公司 | PBT-based luminescent composite material and preparation method thereof |
| CN114940813B (en) * | 2022-06-30 | 2023-07-11 | 广东中塑新材料有限公司 | PBT-based luminous composite material and preparation method thereof |
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